Thioheterocyclic near-infrared absorbing dyes

ABSTRACT

Disclosed is a novel near-infrared absorbing dye of formula: ##STR1## wherein X 1 , X 2  independently represents --CR 8  R 9  --, --S--, --Se--, --NR 10  --, --CH═CH-- or --O--; 
     n is an integer of 2 or 3; 
     R 1  and R 2  independently represent alkyl of 1 to 10 carbons or substituted alkyl of 1 to 10 carbons; 
     R 3  represents a ring chosen from a set consisting of aryl, substituted aryl, and a heterocyclic ring of a type present in photographic emulsions; 
     R 4 , R 5 , R 6  and R 7  independently represent hydrogen, alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, R 4  and R 5  taken together or R 6  and R 7  taken together can represent atoms necessary to form a 5 or 6-membered aliphatic ring, an aromatic six-membered ring, an aromatic 10-membered ring, a substituted aromatic six-member ring or a substituted aromatic 10-member ring; 
     R 8 , R 9  independently represent alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, aryl of 6-10 carbons, or substituted aryl of 6-10 carbons; and 
     R 10  represents an alkyl of 1-10 carbons, substituted alkyl of 1-10 carbons, aryl of 6-10 carbons, or substituted aryl of 6-10 carbons; 
     with the proviso that when R 3  is phenyl or substituted phenyl and n=3, R 1  or R 2  is not an unsubstituted alkyl.

CROSS REFERENCES TO RELATED APPLICATIONS

This is a continuation-in-part application of U.S. patent applicationSer. No. 08/072,851 filed May 26, 1993 U.S. Pat. No. 5,440,042.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to dye technology. More specifically, thistechnology relates to dyes which absorb in the near-infrared.

2. Description of Related Art

The development of the gallium-arsenic semiconductor laser, or diodelaser, is expected to extend the use of lasers into the wavelength rangeof 780-830 nm. The impact of this laser is expected to cover diversefields including opto-electronic systems such as laser optical recordingsystems, thermal writing display systems, laser printing systems, andmedical applications such as cancer treatment and imaging.

Almost any laser application requires some means for absorbing theenergy of the laser beam to accomplish a meaningful task. Fullexploitation of these new lasers awaits the development of near-infraredabsorbing dyes and there has been on ongoing effort in the art toprovide such. Provided herein is a novel class of dyes which absorbthroughout the near-infrared region.

SUMMARY OF THE INVENTION

A novel thioheterocyclic near-infrared absorbing dye is provided offormula ##STR2## wherein

X¹ and X² independently represent --CR⁸ R⁹ --, S, --Se--, --NR¹⁰ --,CH═CH-- or --O--;

n is an integer of 2 or 3;

R¹ and R² independently represent alkyl of 1 to 10 carbons orsubstituted alkyl of 1 to 10 carbons;

R³ represents a ring chosen from a set consisting of aryl, substitutedaryl, and a heterocyclic ring of the type present in photographicemulsions;

R⁴ and R⁵ independently represent hydrogen, alkyl of 1-10 carbons orsubstituted alkyl of 1-10 carbons, or R⁴ and R⁵ taken together representatoms necessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, a substituted aromaticsix-member ring or a substituted aromatic 10-member ring;

R⁶ and R⁷ independently represent hydrogen, alkyl of 1-10 carbons, orsubstituted alkyl of 1-10 carbons, or R⁶ and R⁷ taken together representatoms necessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, a substituted aromaticsix-member ring or a substituted aromatic 10-member ring;

R⁸ and R⁹ independently represent alkyl of 1-10 carbons, substitutedalkyl of 1-10 carbons, aryl of 6-10 carbons or substituted aryl of 6-10carbons;

R¹⁰ represents an alkyl of 1-10 carbons, substituted alkyl of 1-10carbons, aryl of 6-10 carbons or substituted aryl of 6-10 carbons;

Z is a counterion; and

when R³ is phenyl or substituted phenyl and n=3, R¹ or R² is not anunsubstituted alkyl.

DETAILED DESCRIPTION OF THE INVENTION

Dyes of the current invention are defined by the following formula:##STR3## wherein

X¹ and X² independently represent --CR⁸ R⁹ --, --S--, --Se--, --NR¹⁰ --,--CH═CH-- or --O--;

n is an integer of 2 or 3;

R¹ and R² independently represent alkyl of 1 to 10 carbons orsubstituted alkyl of 1 to 10 carbons;

R³ represents a ring chosen from a set consisting of aryl of 6-10carbons, substituted aryl of 6-10 carbons, and a heterocyclic ring of atype present in photographic emulsions;

R⁴ and R⁵ independently represent hydrogen, alkyl of 1-10 carbons, orsubstituted alkyl of 1-10 carbons, or R⁴ and R⁵ taken together representatoms necessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, a substituted aromaticsix-member ring or a substituted aromatic 10-member ring;

R⁶ and R⁷ independently represent hydrogen, alkyl of 1-10 carbons orsubstituted alkyl of 1-10 carbons, or R⁶ and R⁷ taken together representatoms necessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, a substituted aromaticsix-member ring or a substituted aromatic 10-member ring;

R⁸ and R⁹ independently represent alkyl of 1-10 carbons, substitutedalkyl of 1-10 carbons, aryl of 6-10 carbons or substituted aryl of 6-10carbons;

R¹⁰ represents an alkyl of 1-10 carbons, substituted alkyl of 1-10carbons, aryl of 6-10 carbons or substituted aryl of 6-10 carbons;

Z is a counterion; and

when R³ is phenyl or substituted phenyl and n=3, R¹ or R² is not anunsubstituted alkyl.

While not limited thereto a preferred compound is obtained when X¹ or X²is chosen from a set consisting of CR⁸ R⁹, S or NR¹⁰. Most preferred isX¹ or X² being CR⁸ R⁹.

A preferred compound is obtained when R¹ or R² represents an alkyl of 1to 5 carbons and most preferred is R¹ or R² substituted with a sulfonategroup or a carboxyl group.

The term "heterocyclic ring of a type present in photographic emulsions"refers specifically to a heterocyclic nuclei comprising 5 or 6 atoms ina heterocyclic ring. Preferably, R³ represents a heterocyclic ringcomposed of atoms selected from a group consisting of C, N, O, S and Se.Specifically preferred examples of heterocyclic rings of the typespresent in photographic emulsions are chosen from a set consisting of:

the thiazole series; e.g., thiazole, 4-methylthiazole, 4-phenylthiazole,5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,4,5-diphenylthiazole or 4-(2-thienyl)-thiazole;

the benzothiazole series; e.g., benzothiazole, 4-chlorobenzothiazole,5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole,4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole,5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole,6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole,4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole,5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole,5-hydroxybenzothiazole or 6-hydroxybenzothiazole;

the naphthothiazole series; e.g., naphtho[1,2]thiazole,naphtho[2,1]thiazole, 5-methoxynaphtho-[2,1]thiazole,5-ethoxynaphtho[2,1]thiazole, 8-methoxynaphtho[1,2]thiazole or7-methoxynaphtho[1,2]thiazole;

the thianaphtheno-7',6',4,5-thiazole series; e.g.,4'-methoxythianaphtheno-7',6',4,5,thiazole;

the oxazole series; e.g., 4-methyloxazole, 5-methyloxazole,4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole,4,5-dimethyloxazole or 5-phenyloxazole;

the benzoxazole series; e.g., benzoxazole, 5-chlorobenzoxazole,5-methylbenzoxazole, 5-phenylbenzoazole, 6-methylbenzoxazole,5,6-dimethylbenzoxazole, 4,5-dimethylbenzoxazole, 5-methoxybenzoxazole,5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole,5-hydroxybenzoxazole or 6-hydroxybenzoxazole;

the naphthoxazole series, e.g., naphtho[1,2]oxazole,naphtho[2,1]oxazole;

the selenazole series; e.g., 4-methylselenazole or 4-phenylselenazole;

the benzoselenazole series; e.g., benzoselenazole,5-chlorobenzoselenazole, 5-methylbenzoselenazole,5-methoxybenzoselenazole, 5-hydroxybenzoselenazole ortetrahydrobenzoselenazole;

the naphthoselenazole series; e.g., naphthol[1,2]selenazole ornaphtho[2,1]selenazole;

the thiazoline series; e.g., thiazoline, 4-methylthiazoline;

the 2-quinoline series; e.g., quinoline, 3-methylquinoline,5-methylquinoline, 7-methylquinoline, 8-methylquinoline,6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline,6-ethoxyquinoline, 6-hydroxyquinoline or 8-hydroxyquinoline;

the 4-quinoline series; e.g., quinoline, 6-methoxyquinoline,7-methoxyquinoline, 7-methylquinoline or 8-methylquinoline;

the 1-isoquinoline series; e.g., isoquinoline or3,4-dihydroisoquinoline;

the 3-isoquinoline series; e.g., isoquinoline;

the benzimidazole series; e.g., 1,3-diethylbenzimidazole or1-ethyl-3-phenylbenzimidazole;

the 3,3-dialkylindolenine series; e.g., 3,3-dimethylindoline,3,3,5-trimethylindolenine or 3,3,7-trimethylindolenine;

the 2-pyridine series; e.g., pyridine or 5-methylpyridine;

the 4-pyridine series; e.g., pyridine;

the 3,3-dialkylbenz[e]indole series; e.g., 3,3-dimethylbenz[e]indole;

the tetrazole series; e.g., 1-phenyltetrazole or 1-methyltetrazole;

the triazole series; e.g., 1-phenyl-triazole or 1-methyltriazole;

the pyrimidine series; e.g., pyrimidine; and

the thiadiazole series; e.g., 1,3,4-thiadiazole.

Preferred compounds are obtained when R³ is chosen from a set consistingof:

the thiazole series; e.g., thiazole, 4-methylthiazole, 4-phenylthiazole,5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,4,5-diphenylthiazole or 4-(2-thienyl)-thiazole;

the benzothiazole series; e.g., benzothiazole, 4-chlorobenzothiazole,5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole,4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole,5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole,6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole,4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole,5,6-dimethoxybenzothiazole, 5-dioxymethylenebenzothiazole,5-hydroxybenzothiazole or 6-hydroxybenzothiazole;

the benzoxazole series; e.g., benzoxazole, 5-chlorobenoxazole,5-methylbenzoxazole, 5-phenylbenzoazole, 6-methylbenzoxazole,5,6-dimethylbenzoxazole, 4,5-dimethylbenzoxazole, 5-methoxybenzoxazole,5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole,5-hydroxybenzoxazole or 6-hydroxybenzoxazole;

the benzimidazole series; e.g., 1,3-diethylbenzimidazole or1-ethyl-3-phenylbenzimidazole;

the tetrazole series; e.g., 1-phenyltetrazole or 1-methyltetrazole;

the triazole series; e.g., 1-phenyl-triazole or 1-methyltriazole;

the pyrimidine series; e.g., pyrimidine; and

the thiadiazole series; e.g., 1,3,4-thiadiazole.

The term "alkyl" is used herein in a manner consistent with the art todescribe a straight chain or branched hydrocarbon group. The term "aryl"is used herein in a manner consistent with the art to describe anaromatic cyclic six-membered ring such as a phenyl group or an aromatic10-membered ring such as a naphthalene group. The term "substitutedalkyl", as used herein, specifically refers to a straight or branchedalkyl which is substituted with at least one group such as sulfonate,carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL, where Lis an alkyl or substituted alkyl of 1-10 carbons. The most preferredsubstituent for alkyl is sulfonate or carboxyl. The term "substitutedaryl", as used herein, specifically refers to a six- or 10-membered ringwhich is substituted with at least one group such as sulfonate,carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or --OL, where Lis an alkyl or substituted alkyl of 1-10 carbons. The most preferredsubstituent for aryl is sulfonate or carboxylate. The term aromaticsix-membered ring refers to atoms chosen from C, N, O and S necessary toform an aromatic ring. Specifically, preferred examples include phenyl,pyridine, pyrimidine, pyrazine, and pyridazine. The term aromatic10-membered ring refers to atoms chosen from C, N, O and S necessary tofrom an aromatic 10-membered ring. Specific examples include quinoline,naphthalene, phthalazine, naphthyridine, quinoxaline, quinazoline,cinnoline, and pteridine. The term 5 or 6-membered aliphatic ring refersto elements C, N, O and S necessary to form an aliphatic ring. Specificexamples include cyclopentane, cyclopentene, cyclohexane, cyclohexene,furan, pyran, pyrrole, pyrroline, pyrrolidine, piperidine, andpiperizine.

The term "counterion", or the equivalent thereto, refers to an anion orcation suitable to balance the charge. Preferred counterions includehalide, alkaline earths, a complex inorganic ion (e.g., perchlorate), acommon organic ion (e.g., tetrafluoroborate or tetraalkylammonium), oran anion of a strong acid (e.g., toluene sulfonate). Most preferably,counterions are chosen from a set consisting of sodium, potassium,chloride, bromide, iodide, CF₃ SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, P--CH₃ C₆ H₄ SO₃ ⁻and D₄ N⁺ where D is a hydrogen or an alkyl of 1 to 10 carbons.

Exemplary dyes are provided in Table 1. Within Table 1, Y is defined bythe following structures: ##STR4##

When BMTD is used, the dye is in a form of a dimer with BMTD acting as abridging group between two chromophores.

Dyes of the current invention are prepared by known organic preparativetechniques in accordance with the following synthetic reaction: ##STR5##wherein R¹, R³, R⁴, R⁵, X¹, n and Z are as defined above. One ofordinary skill in the art would appreciate that the unsymmetrical dyecould be prepared in an analogous manner by substituting one mole of thecyclic amine with a second cyclic amine as known in the art.

The choice of cyclic amine represented by: ##STR6## will determine theterminal rings of the final dye. As such when X¹ or X² is intended to beCR⁸ R⁹ the proper starting material is an appropriately substitutedpyrrole or indole; when X¹ or X² is intended to be --S-- the properstarting material is an appropriately substituted thiazole,benzothiazole or naphthothiazole; when X¹ or X² is intended to be --Se--the proper starting material is an appropriately substituted selenazole,benzoselenazole or naphthselenazole; when X¹ or X² is intended to be--NR-- the proper starting material is an appropriately substitutedimidazole, benzimidazole, or naphthimidazole; when X¹ or X² is intendedto be --CH═CH-- the proper starting material is an appropriatelysubstituted pyridine, quinoline or benzquinoline; and when X¹ or X² isintended to be --O-- the proper starting material is an appropriatelysubstituted oxazote, benzoxazole or naphthoxazole.

The following detailed synthetic procedures are not intended to belimiting in any way. Other compounds described herein can be prepared inan analogous manner using standard organic synthetic procedures as knownin the art.

STARTING MATERIALS

The following starting materials are used in the synthesis of the dyes.

Compound A

3H-Indolium,2-[2-[2-chloro-3[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene]-1-cyclopenten-1yl]ethenyl]-1,3,3-trimethyl-,salt with trifluoromethanesulfonic acid (1:1) is disclosed in Laganisand West, U.S. Pat. No. 4,882,265.

Compound B

1-(4-Sulfobutyl)-2,3,3-trimethylindolenium, inner salt

2,3,3-Trimethylindolenine (16.0 g, 0.01 mol) was heated with 10.4 mlmelted 1,4-butanesultone and 20 ml o-xylene at 146° C. for 4 hours. Theorange solution was cooled to 60° C. before adding acetone to dilute andinduce crystallization. After cooling to room temperature, the productwas collected by filtration, washed with acetone, and dried to yield22.15 g of quaternary salt, mp 236° C.

Compound C

2-Chloro-3-(anilinomethylene)-1-(aniliniummethyl)cyclopent-1-enehydrochloride is disclosed by reference to Laganis and West, U.S. Pat.No. 4,882,265 and by reference to E.P. 0 420 012 A1.

Compound D

Compound B (4.58 g, 0.0155 mol), Compound C (2.69 g, 0.00775 mol), and60 ml dimethylformamide were mixed together. Acetic anhydride (4.14 ml)was added, followed by 2.4 g (0.024 mol) triethylamine. The mixture wasstirred at room temperature for 5.5 hrs. and then cooled to 0° C. beforefiltering. The filtrate was poured into 300 ml of stirred ethyl acetateand then chilled. After stirring overnight, the mixture was filtered andthe recovered solid reslurried twice with ethyl acetate. After filteringand drying, the yield was 4.25 g, mp 210° C., λ_(max) (methanol)=806(ε=265,000).

Compound E

2-Chloro-3-(hydroxymethylene)-1-formylcyclohex-1-ene

Dimethylformamide (40 ml) and 40 ml dichloromethane were mixed andcooled to 5° C. Phosphorous oxychloride (33 ml) was dissolved in 40 mldichloromethane and added dropwise to thedimethylformamide/dichloro-methane solution at a rate sufficient tomaintain the temperature below 25° C. Cyclohexanone (9 g) was added andthe mixture heated to reflux for 5 hours. After cooling to roomtemperature, the reaction mixture was poured into 200 ml of ice andallowed to sit overnight. The quenched mixture was filtered to collect9.62 g yellow crystals, mp 128° C., λ_(max) (methanol)=328 nm(ε=15,000).

Compound F

Compound E (2.16 g, 0.0125 mol), Compound B (7.38 g, 0.025 mol), and 30ml acetic acid were mixed together. Acetic anhydride (7 ml) was added,followed by 2.05 g (0.025 mol) anhydrous sodium acetate. The mixture washeated to reflux for 30 min., then cooled to room temperature andfiltered. The filtrate was poured into 300 ml ethyl acetate and allowedto sit 3 hours. The solvent was decanted and replaced by fresh ethylacetate. The mixture was agitated to break up the solid, filtered, andthe residue reslurried twice with ethyl acetate. After filtering anddrying, the yield was 6.55 g, mp 222° C. (dec), λ_(max) (methanol)=782nm (ε=227,000).

Compound G

2,3,3-Trimethyl-(4-sulfobutyl)-1H-benzindolium, inner salt

1,1,2-Trimethyl-1H-benzindole (184.47 g, 0.88 mol) was heated with 91.8ml liquid 1,4-butanesultone and 600 ml o-xylene at 144°-148° C. for 7.5hours. The greenish solution was cooled to 70° C. before adding 200 mlacetone to dilute and induce crystallization. After cooling to 13° C.,the product was collected by filtration, washed with acetone, andslurried twice in acetone. After filtering and drying, the yield was193.10 g of quaternary salt, mp 222° C.

Compound H

Compound G (171 g, 0.05 mol), Compound C (86 g, 0.25 mol), and 2000 mldimethylformamide were mixed together. Acetic anhydride (100 ml) wasadded. To the stirred mixture was added 75.5 g (0.75 mol) triethylamine.The mixture was carefully heated and held between 83°-90° C. for no morethan 6 minutes. The reaction cooled quickly with a methanol-ice bath to-3° C. The mixture was filtered to removed unreacted starting materialand the filtrate was then poured into 5000 ml of ethyl acetate. Themixture was chilled and stirred for at least three hours, then filtered,and the isolated product reslurried in ethyl acetate. After filtrationand drying, the yield was 173.10 g, mp 241° C., λ_(max) (methanol)=845nm (ε=250,000). A second crop of dye was recovered after letting theinitial ethyl acetate quench sit overnight: 4.75 g, mp 249° C., λ_(max)(methanol)=845 nm (ε=289,000).

Compound I

Compound E (1.72 g, 0.01 mol),6-Sulfo-1-(4-sulfobutyl)-2,3,3-trimethyl-1H-benzindolium, inner salt(NKX-1632 from Nippon Kankoh Shikiso, 8.27 g, 0.02 mol), and 30 mlacetic acid were mixed together. Acetic anhydride (7 ml) was added,followed by 4.1 g (0.05 mol) anhydrous sodium acetate. The mixture washeated to reflux for 21 min., then cooled to room temperature andfiltered. The filtrate was poured into 300 ml ethyl acetate and allowedto sit overnight. The solvent was decanted and replaced by fresh ethylacetate. The mixture was agitated to break up the solid, filtered anddried. The yield was 9.20 g, mp>350° C., λ_(max) (methanol)=821 nm(ε=226,000).

Compound J

Compound E (2.16 g, 0.0125 mol),5-Sulfo-1-(4-Sulfobutyl)-2,3,3-trimethylindolenium, inner salt (NKX-1653from Nippon Kankoh Shikiso, 9.38 g, 0.025 mol), and 30 ml acetic acidwere mixed together. Acetic anhydride (7 ml) was added, followed by 4.1g (0.05 mol) anhydrous sodium acetate. The mixture was heated to refluxfor 20 min., then cooled to room temperature and filtered. The filtratewas poured into 300 ml ethyl acetate to copiously precipitate solid.After stirring three hours, the mixture was filtered and the productreslurried in 150 ml ethyl acetate overnight. After filtering anddrying, the yield was 13.55 g., mp 298° C. (dec), λ_(max) (methanol)=789nm (ε=197,000).

Compound K

Compound C (4.3 g, 0.0125 mol),5-Sulfo-1-(4-Sulfobutyl)-2,3,3-trimethylindolenium, inner salt (NKX-1653from Nippon Kankoh Shikiso, 9.38 g, 0.025 mol), and 60 mldimethylformamide were mixed together. Acetic anhydride (6.6 ml) wasadded, followed by 5.6 g (0.055 mol) triethylamine. The mixture wasstirred at room temperature for 4.5 hours. The reaction mixture wasfiltered and the filtrate was poured into 200 ml ethyl acetate. Afterstirring at least one hour, the mixture was filtered and the productreslurried in ethyl acetate. After filtering and drying, the yield was11.91 g., mp 154°-187° C., λ_(max) (methanol)=811 nm (ε=251,000).

Compound L

3-Ethyl-2-methylbenzothiazolium iodide (I1003 from H. W. Sands, 2.44 g,0.008 mol), Compound C (1.38 g, 0.04 mol), and 30 ml dimethylformamidewere mixed together. Acetic anhydride (2.0 ml) was added, followed by1.2 g (0.012 mol) triethylamine. The mixture was stirred at roomtemperature for 3 hrs. and then filtered. The collected gold-browncrystals were slurried overnight with ethyl acetate. After filtering anddrying, the yield was 1.80 g, mp 222° C., λ_(max)(methanol)=807(ε=196,000).

Compound M

1,3-Diallyl-2-methyl-4,5-quinoxalino-imidazolium 4-toluenesulfonate

2,3-Bis-(3-allylamino)quinoxalinium 4-toluenesulfonate (16.48 g),prepared by reaction of allylamine with 2,3-dichloroquinoxaline, wasrefluxed with 40 ml acetic anhydride for two hours. After cooling toroom temperature, the reaction mixture was poured into 300 ml of stirreddiethyl ether. The resulting precipitate was broken up and trituratedwith ether until fine particles were obtained. Yield was 12.63 g, mp158° C.

Compound N

Compound M (17.46 g, 0.04 mol), Compound C (6.88 g, 0.02 mol), and 200ml dimethylformamide were mixed together. Acetic anhydride (10.4 ml) wasadded, followed by 6.0 g (0.06 mol) triethylamine. The mixture wasstirred at room temperature for 4.5 hrs. and then filtered. The filtratewas poured into 2000 ml of water, stirred for an hour, and filtered. Theproduct was reslurried in ethyl acetate, filtered and dried to yield14.31 g, mp 165°-173° C., λ_(max) (1% acetic acid/methanol)=846 nm(ε=165,000).

SYNTHESIS OF DYE COMPOUNDS

Dye D-1

2,5-Dimercapto-1,3,4-thiadiazole, dipotassium salt (0.45 g, 0.002 mol)was mixed with 20 ml DMF. To this mixture was added 2.48 g (0.004 mol)of Compound A. After 1 hour, the reaction mixture was filtered and thenpoured into 200 ml of stirred water. After 60 minutes of stirring, themixture was filtered and the collected dye dried to give 2.28 g dye, mp208° C., λ_(max) (methanol)=741 nm (ε=241,000), 813 (ε=207,000).

Dye D-2

2-Mercaptopyrimidine (0.3 g, 0.0027 mol) was mixed with 10 ml DMF.Triethylamine (0.27 g, 0.0027 mol) was added. To this mixture was added1.0 g (0.00134 mol) of Compound F. The reaction was instantaneous. Thereaction mixture was filtered and then poured into 200 ml of stirredethyl acetate. After 60 minutes of stirring, the mixture was filtered.The product was collected, washed again with ethyl acetate, filtered anddried to give 1.08 g. dye, mp 120°-195° C. (dec), λ_(max) (methanol)=798nm (ε=170,000).

Dye D-3

2-Benzoxazolethiol (0.6 g, 0.004 mol) was mixed with 10 ml DMF.Triethylamine (0.4 g, 0,004 mol) was added. To this mixture was added1.5 g (0.002 mol) of Compound F. The reaction mixture was stirred 6.5hrs at room temperature, then filtered and poured into 200 ml of stirredethyl acetate. After 60 minutes of stirring, the mixture was filtered.The product was collected, washed again with ethyl acetate, filtered anddried to give 1.43 g dye, mp 195°-203° C. (dec), λ_(max) (methanol)=802nm (ε=207,000).

Dye D-4

4-Acetamidothiophenol (0.67 g, 0.004 mol) was mixed with 10 ml DMF.Sodium hydroxide (0.32 g, 0.008 mol) in 1 ml water was added. To thismixture was added 1.91 g (0.002 mol) of Compound J. The reaction wasstirred for forty minutes at room temperature. The reaction mixture wasfiltered and then poured into 200 ml of stirred ethyl acetate. Afterstirring one hour, the mixture was filtered and reslurried with ethylacetate. After filtering and drying, the yield was 2.54 g, mp 245°-258°C., λ_(max) (methanol)=801 nm (ε=128,000). A purer sample was obtainedby slurrying 1 g of the product in ethyl acetate, adding 1 mlconcentrated hydrochloric acid to coagulate, decanting the solvent andredissolving the residue in methanol. The methanol solution was pouredinto 100 ml stirred ethyl acetate. After stirring 3 hours, theprecipitate was collected by filtration, washed with ethyl acetate, anddried to yield 0.87 g, mp 272° C. (dec), λ_(max) (methanol)=802 nm(ε=149,000).

Dye D-5

2-Mercaptopyrimidine (0.45 g, 0.004 mol) was mixed with 10 ml DMF.Sodium hydroxide (0.16 g, 0.004 mol) in 0.5 g water was added. To thismixture was added 1.91 g (0.002 mol) of Compound J. The reaction wasstirred 2 hrs at room temperature. The reaction mixture was filtered andthen poured into 200 ml of stirred ethyl acetate. After stirring twohours, the mixture was filtered and reslurried with ethyl acetate. Afterfiltering and drying, the yield was 2.12 g., 310° C. (dec), λ_(max)(methanol)=803 nm (ε=133,000).

Dye D-6

1-phenyl-1H-tetrazole-5-thiol, sodium salt (0.8 g, 0.004 mol) was mixedwith 10 ml DMF. To this mixture was added 1.5 g (0.002 mol) of CompoundF. The reaction mixture was stirred 4 hrs at room temperature, thenfiltered and then poured into 200 ml of stirred ethyl acetate. After 60minutes of stirring, the mixture was filtered. The product wascollected, washed again with ethyl acetate, filtered and dried to give1.64 g dye, mp 180° C. (dec), λ_(max) (methanol) =806 nm (ε=169,000).

Dye D-7

4-Methyl-4H,1,2,4-triazole-3-thiol (0.46 g, 0.004 mol) was mixed with 20ml DMF. Sodium hydroxide (0.16 g, 0.004 mol) in 1 ml water was added. Tothis mixture was added 1.91 g (0.002 mol) of Compound J. The reactionwas stirred one hour at room temperature. The reaction mixture wasfiltered and then poured into 200 ml of stirred ethyl acetate. Afterstirring one hour, the mixture was filtered and reslurried with ethylacetate. After filtering and drying, the yield was 1.75 g, 310° C.(dec), λ_(max) (methanol)=809 nm (ε=84,000).

Dye D-8

2-Benzoxazolethiol (0.61 g, 0.004 mol) was mixed with 10 ml DMF. Sodiumhydroxide (0.16 g, 0.004 mol) in 0.5 ml water was added. To this mixturewas added 1.91 g. (0.002 mol) of Compound J. The reaction was stirred3.5 hrs at room temperature. The reaction mixture was filtered and thenpoured into 200 ml of stirred ethyl acetate. After stirring two hours,the mixture was filtered and reslurried with ethyl acetate. Afterfiltering and drying, the yield was 1.71 g, 325° C. (dec), λ_(max)(methanol)=809 nm (ε=148,000).

Dye D-9

3-Amino-5-mercapto-1,2,4-triazole(0.93 g, 0.008 mol) was mixed with 20ml DMF. To this mixture was added 2.48 g (0.004 mol) of Compound A.After 3.5 hours, the reaction mixture was filtered and then poured into200 ml of stirred water. After 60 minutes of stirring, the mixture wasfiltered. The dye was collected and dried to give 2.36 g dye, mp 216°C., λ_(max) (methanol)=811 nm (ε=132,000).

Dye D-10

4-Acetamidothiophenol (2.68 g, 0. 016 mol) was mixed with 40 ml DMF. Asolution of 0.64 g (0.016 mol) sodium hydroxide in 2 ml water was added.To this mixture was added 4.96 g (0.008 mol) of Compound A. After 1hour, the reaction mixture was filtered and then poured into 200 ml ofstirred water. After 60 minutes of stirring, the mixture was filtered.The product was collected and dried to give 6.69 g crude dye, mp70°-105° C., λ_(max) (methanol)=811 nm (ε=172,000).

Dye D-11

1-Phenyl-1H-tetrazole-5-thiol, sodium salt (0.80 g, 0.004 mol) was mixedwith 10 ml DMF. To this mixture was added 1.91 g (0.002 mol) of CompoundJ. The reaction was stirred 27 hrs at room temperature. The reactionmixture was filtered and then poured into 200 ml of stirred ethylacetate. After stirring three hours, the mixture was filtered andreslurried with ethyl acetate. After filtering and drying, the yield was0.80 g, 300° C. (dec), λ_(max) (methanol)=813 nm (ε=196,000).

Dye D-12

2,5-Dimercapto-1,3,4-thiadiazole, dipotassium salt (1.8 g, 0.008 mol)was mixed with 20 ml DMF. To this mixture was added 2.48 g (0.004 tool)of Compound A. After 1 hour, the reaction mixture was filtered and thenpoured into 200 ml of stirred water. After 60 minutes of stirring, themixture was filtered and the collected dye dried to give 1.44 g dye, mp215° C., λ_(max) (methanol)=819 nm (ε=257,000).

Dye D-113

2-Mercaptopyrimidine (0.9 g, 0.008 mol) was mixed with 20 ml DMF. Asolution of 0.32 g (0.008 mol) sodium hydroxide in 0.32 ml water wasadded. To this mixture was added 2.48 g (0.004 mol) of Compound A. Theabsorption of the solution instantaneously shifted from 797 nm to 819nm. The reaction mixture was filtered and then poured into 200 ml ofstirred water. After 60 minutes of stirring, the mixture was filteredand the collected dye dried to give 2.49 g dye, mp 245° C., λ_(max)(methanol)=819 nm (ε=229,000).

Dye D-14

2-Mercaptobenzimidazole (1.2 g, 0.008 mol) was mixed with 20 ml DMF. Asolution of 0.32 g (0.008 mol) sodium hydroxide in 0.32 ml water wasadded. To this mixture was added 2.48 g (0.004 mol) of Compound A. Theabsorption of the solution instantaneously shifted from 797 nm to 814nm. The reaction mixture was filtered and then poured into 200 ml ofstirred water. After 60 minutes of stirring, the mixture was filteredand the collected dye reslurried with isopropanol. After filtering anddrying, the yield was 1.48 g dye, mp 211°-215° C., λ_(max)(methanol)=819 nm (ε=38,000).

Dye D-15

4-Methyl-4H-1,2,4-triazole-3-thiol (0.92 g, 0.008 mol) was mixed with 20ml DMF. Triethylamine (0.81 g, 0.008 mol) was added. To this mixture wasadded 2.48 g (0.004 mol) of Compound A. After 50 minutes, the reactionmixture was filtered and then poured into 200 ml of stirred water. After60 minutes of stirring, the mixture was filtered. The product wascollected and dried to give 2.52 g dye, mp 149°-165° C., λ_(max)(methanol)=822 nm (ε=226,000).

Dye D-16

2-Mercaptopyrimidine (0.34 g, 0.003 mol) was mixed with 10 ml DMF. Tothis mixture was added 0.30 g (0.003 mol) triethylamine. After mixingwell, Compound D (0.91 g, 0.001 mol) was added. The reaction wasinstantaneous. The reaction mixture was filtered and then poured into200 ml of stirred ethyl acetate. After 120 minutes of stirring, themixture was filtered. The product was collected, washed again with ethylacetate, filtered and dried to give 0.76 g dye, mp 134°-145° C., λ_(max)(methanol)=823 nm (ε=220,000).

Dye D-17

4-Acetamidothiophenol (0.67 g, 0.004 mol) was mixed with 10 ml DMF.Triethylamine (0.404 g, 0.004 mol) was added. To this mixture was added2.35 g (0.002 mol) of Compound K. The reaction was stirred for fortyminutes at room temperature. The solvent was decanted and the residuedissolved in methanol. The solution was treated with 10 ml of 20%potassium acetate in methanol. The product immediately precipitated.After filtering and drying, the yield was 1.30 g, mp 310°, λ_(max)(methanol)=823 nm (ε=164,000 ).

Dye D-18

2-Benzoxazolethiol (30.2 g, 0.02 mol) was mixed with 500 mldimethylformamide (DMF). A solution of 8.0 g (0.2 mol) sodium hydroxidein 16 ml water was added. To this mixture was added 62 g (0.1 mol) ofCompound A. The absorption of the solution instantaneously shifted from797 nm to 823 nm. The reaction mixture was filtered and then poured into1000 ml of stirred water. After 60 minutes of stirring, the mixture wasfiltered and the product vacuum-dried. The dry dye was stirred 60minutes with 200 ml methanol, filtered, and air-dried to give 49.31 g.dye, mp 139°-141° C., λ_(max) (methanol)=825 nm (ε=211,000).

Dye D-19

2-Mercaptobenzothiazole (1.34 g, 0.008 mol) was mixed with 20 ml DMF. Asolution of 0.32 g (0.008 mol) sodium hydroxide in 0.32 ml water wasadded. To this mixture was added 2.48 g (0.004 mol) of Compound A. After1 hour, the reaction mixture was filtered and then poured into 200 ml ofstirred water. After 60 minutes of stirring, the mixture was filtered.The dye was collected and dried to give 3.12 g, mp 70°-85° C., λ_(max)(methanol)=825 nm (ε=183,000).

Dye D-20

5-Mercapto-1-methyltetrazole sodium salt hydrate (1.11 g, 0.008 mol) wasmixed with 20 ml DMF. To this mixture was added 2.48 g (0.004 mol) ofCompound A. After 2.5 hours, the reaction mixture was filtered and thenpoured into 200 ml of stirred water. After 60 minutes of stirring, themixture was filtered. The product was collected and dried to give 2.67 gdye. The crude dye was rewashed with 5% aqueous sodium carbonate,filtered, and dried to give 2.44 g, mp 125°-144° C., λ_(max)(methanol)=828 nm (ε=196,000).

Dye D-21

Compound A (1.24 g, 0.002 mol) was mixed with1-phenyl-1H-tetrazole-5-thiol, sodium salt (0.752 g, 0.004 mol) in 10 mldimethylformamide (DMF). The absorption of the solution instantaneouslyshifted from 797 nm to 830 nm. The reaction mixture was filtered, thenpoured into 200 ml ether. The solvent was decanted and the residual oilrinsed with both ether and water. The oil was treated with a smallamount of methanol to solidify, then filtered and washed withisopropanol to collect 1.10 g golden crystals, mp 133°-140° C., λ_(max)(methanol)=829 nm (ε=197,000).

Dye D-22

Compound A (2.48 g, 0.004 mol) was mixed with1-(4-hydroxyphenyl-1H-tetrazole-5-thiol (ORWO OB-1209, 1.55 g, 0.008mol) in 20 ml dimethylformamide (DMF) and 0.32 g sodium hydroxide in 1ml water. The absorption of the solution instantaneously shifted from797 nm to 829 nm. The reaction mixture was stirred for 20 min.,filtered, and then poured into 200 ml 5% aqueous potassium carbonate.The mixture was stirred for two hours and filtered. The collectedproduct was taken up in acetone, stirred, and filtered to yield 0.77 g,mp 197° C., λ_(max) =829 nm (ε=211,000). The acetone rinsings werepoured into 500 ml of 1% aqueous potassium carbonate, stirred 3 hours,filtered, and the product dried to give 1.58 g additional dye, mp173°-177° C., λ_(max) =828 nm (ε=203,000).

Dye D-23

1-Phenyl-1H-tetrazole-5-thiol, sodium salt (1.6 g, 0.008 mol) was mixedwith 10 ml DMF. To this mixture was added 1.47 g (0.002 mol) of CompoundD. The reaction was instantaneous. The reaction mixture was filtered andthen poured into 200 ml of stirred ethyl acetate. After 60 minutes ofstirring, the mixture was filtered. The product was collected, washedagain with ethyl acetate, filtered and dried to give 0.50 g dye, mp 185°C. (dec), λ_(max) (methanol)=838 nm (ε=164,000).

Dye D-24

2-Mercaptopyrimidine (0.45 g, 0.004 mol) was mixed with 10 ml DMF.Sodium hydroxide (0.16 g, 0.004 mol) in 0.5 g water was added. To thismixture was added 2.1 g (0.002 mol) of Compound I. The reaction wasstirred 5.5 hrs at room temperature. The reaction mixture was filteredand then poured into 200 ml of stirred ethyl acetate. After stirringovernight, the mixture was filtered and reslurried twice with ethylacetate. After filtering and drying, the yield was 2.18 g., mp>350° C.(dec), λ_(max) (methanol)=834 nm (ε=199,000).

Dye 25

2,5-Dimercapto-1,3,4-thiadiazole, dipotassium salt (0.23 g, 0.001 mol)was mixed with 20 ml DMF. To this mixture was added 2.10 g (0.002 mol)of Compound I. The reaction was stirred 5.5 hrs at room temperature,then 0.33 g sodium hydroxide in 1 ml water was added. The mixture wasstirred 16 hrs. at room temperature, then filtered. The filtrate waspoured into 200 ml of stirred ethyl acetate. After stirring two hours,the mixture was filtered and reslurried with ethyl acetate. Afterfiltering and drying, the yield was 2.15 g., 301° C. (dec), λ_(max)(methanol)=836 nm (ε=234,000), 765 nm (ε=134,000).

Dye D-26

1-phenyl-1H-tetrazole-5-thiol, sodium salt (0.8 g, 0,004 mol) was mixedwith 10 ml DMF. To this mixture was added 0.91 g (0.001 mol) of CompoundH. The reaction was instantaneous. The reaction mixture was filtered andthen poured into 100 ml of stirred ethyl acetate. After 60 minutes ofstirring, the mixture was filtered. The product was collected, washedagain with ethyl acetate, filtered and dried to give 0.55 g dye, mp 285°C., λ_(max) (methanol)=879 nm (ε=252,000).

Dye D-27

1-Phenyl-1H-tetrazole-5-thiol, sodium salt (0.4 g, 0.002 mol) was mixedwith 10 ml DMF. To this mixture was added 0.6 g (0.00099 mol) CompoundL. After stirring six hours at room temperature, the reaction mixturewas filtered. The collected product was slurried with ethyl acetate,filtered and dried to give 0.48 g dye, mp 233°-234° C., λ_(max)(methanol)=844 nm (ε=209,000).

Dye D-28

1-Phenyl-1H-tetrazole-5-thiol, sodium salt (0.42 g, 0.002 mol) was mixedwith 10 ml DMF. To this mixture was added 0.78 g (0.001 mol) Compound N.After stirring 1.6 hours at room temperature, the reaction mixture wasfiltered. The filtrated was poured into 200 ml 5% aqueous potassiumcarbonate, stirred for three hours, then filtered and dried to give 0.69g dye, mp 138°-143° C. (dec), λ_(max) (1% acetic acid/methanol)=874 nm(ε=121,000).

                                      TABLE 1                                     __________________________________________________________________________    EXEMPLARY DYES                                                                __________________________________________________________________________    INDOLENINE                                                                     ##STR7##                                                                                                      λ.sub.max nm                          DYE X    R       Y     Z      n  (ε × 10.sup.-5)                __________________________________________________________________________    D-1 H    CH.sub.3                                                                              BMTD  CF.sub.3 SO.sub.3.sup.-                                                              2  741 (2.41)                                                    (2:1)*          813 (2.07)                                   D-2 H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PYR   (Et.sub.3 NH.sup.+)                                                                  3  798 (1.69)                                   D-3 H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       MBO   (Et.sub.3 NH.sup.+)                                                                  3  802 (2.07)                                   D-4 SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       SAR   3Na.sup.+                                                                            3  802 (1.49)                                   D-5 SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PYR   3Na.sup.+                                                                            3  803 (1.33)                                   D-6 H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PMT   Na.sup.+                                                                             3  806 (1.69)                                   D-7 SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       MTT   3Na.sup.+                                                                            3  809 (0.83)                                   D-8 SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       MBO   3Na.sup.+                                                                            3  809 (1.48)                                   D-9 H    CH.sub.3                                                                              AMT   CF.sub.3 SO.sub.3.sup.-                                                              2  811 (1.31)                                   D-10                                                                              H    CH.sub.3                                                                              SAR   CF.sub.3 SO.sub.3.sup.-                                                              2  811 (1.71)                                   D-11                                                                              SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PMT   3Na.sup.+                                                                            3  813 (1.96)                                   D-12                                                                              H    CH.sub.3                                                                              BMTD  CF.sub.3 SO.sub.3.sup.-                                                              2  819 (2.57)                                                    (1:1)**                                                      D-13                                                                              H    CH.sub.3                                                                              PYR   CF.sub.3 SO.sub.3.sup.-                                                              2  819 (2.29)                                   D-14                                                                              H    CH.sub.3                                                                              MBI   CF.sub.3 SO.sub.3.sup.-                                                              2  819 (0.38)                                   D-15                                                                              H    CH.sub.3                                                                              MTT   CF.sub.3 SO.sub.3.sup.-                                                              2  823 (2.18)                                   D-16                                                                              H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PYR   (Et.sub.3 NH.sup.+)                                                                  2  823 (2.19)                                   D-17                                                                              SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       SAR   3K.sup.+                                                                             2  823 (1.64)                                   D-18                                                                              H    CH.sub.3                                                                              MBO   CF.sub.3 SO.sub.3.sup.-                                                              2  825 (2.11)                                   D-19                                                                              H    CH.sub.3                                                                              MBT   CF.sub.3 SO.sub.3.sup.-                                                              2  825 (1.83)                                   D-20                                                                              H    CH.sub.3                                                                              MMTE  CF.sub.3 SO.sub.3.sup.-                                                              2  828 (1.96)                                   D-21                                                                              H    CH.sub.3                                                                              PMT   CF.sub.3 SO.sub.3.sup.-                                                              2  829 (1.97)                                   D-22                                                                              H    CH.sub.3                                                                              HPMT  CF.sub.3 SO.sub.3.sup.-                                                              2  829 (2.11)                                   D-23                                                                              H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PMT   Na.sup.+                                                                             2  838 (1.64)                                   __________________________________________________________________________    BENZINDOLES                                                                    ##STR8##                                                                                                      λ.sub.max                             DYE X    R       Y     Z      n  (ε × 10.sup.-5)                __________________________________________________________________________    D-24                                                                              SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PYR   3Na.sup.+                                                                            3  834 (2.00)                                   D-25                                                                              SO.sub.3.sup.-                                                                     (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       BMTD  3Na.sup.+                                                                            3  836 (2.34)                                                    (2:1)*          736(1.33)                                    D-26                                                                              H    (CH.sub.2).sub.4 SO.sub.3.sup.-                                                       PMT   Na.sup.+                                                                             2  879 (2.52)                                   __________________________________________________________________________    BENZOTHIAZOLE                                                                  ##STR9##                                                                     D-27 λ.sub.max = 844 nm (ε = 209,000)                          OUINOXALINE                                                                    ##STR10##                                                                    D-28 λ.sub.max = 874 nm (ε = 121,000)                          __________________________________________________________________________     *Two thioether links                                                          **One thioether link                                                     

What is claimed is:
 1. A dye of formula: ##STR11## wherein X¹ and X²independently represents --O--;n is an integer of 2 or 3; R¹ and R²independently represent alkyl of 1 to 10 carbons or an alkyl of 1 to 10carbons substituted with at least one substituent chosen from a groupconsisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl,amine, aryl or --OL¹, where L¹ is an alkyl of 1-10 carbons; R³represents an aryl ring, or an aryl substituted with at least onesubstituent chosen from a group consisting of sulfonate, carboxyl,hydroxy, halogen, carbonylalkyl, amine, aryl or --OL², where L² is analkyl of 1-10 carbons; R⁴ and R⁵ independently represent hydrogen, alkylof 1-10 carbons or an alkyl of 1-10 carbons substituted with at leastone substituent chosen from a group consisting of sulfonate, carboxyl,hydroxy, halogen, carbonylalkyl, amine, aryl or --OL³, where L³ is analkyl of 1-10 carbons, or R⁴ and R⁵ taken together represent the atomsnecessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, an aromatic six-memberring substituted with at least one substituent chosen from a groupconsisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl,amine, aryl or --OL⁴, where L⁴ is an alkyl of 1-10 carbons or anaromatic 10-member ring substituted with at least one substituent chosenfrom a group consisting of sulfonate, carboxyl, hydroxy, halogen,carbonylalkyl, amine, aryl or --OL⁵, where L⁵ is an alkyl of 1-10carbons; R⁶ and R⁷ independently represent hydrogen, alkyl of 1-10carbons or an alkyl of 1-10 carbons substituted with at least onesubstituent chosen from a group consisting of sulfonate, carboxyl,hydroxy, halogen, carbonylalkyl, amine, aryl or --OL⁶, where L⁶ is analkyl of 1-10 carbons, or R⁶ and R⁷ taken together represent atomsnecessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, an aromatic six-memberring substituted with at least one substituent chosen from a groupconsisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl,amine, aryl or --OL⁷, where L⁷ is an alkyl of 1-10 carbons or anaromatic 10-member ring substituted with at least one substituent chosenfrom a group consisting of sulfonate, carboxyl, hydroxy, halogen,carbonylalkyl, amine, aryl or --OL⁸, where L⁸ is an alkyl of 1-10carbons; and Z is an anion or cation suitable to balance the charge. 2.The dye recited in claim 1, wherein at least one of R¹ and R² is analkyl of 1 to 10 carbon atoms substituted with sulfonate or carbonate.3. The dye recited in claim 1, wherein R4 and R5 or R6 and R7 are takentogether to form a six-membered aromatic ring or a 10-membered aromaticring.
 4. The dye recited in claim 3, wherein said six-membered aromaticring or said 10-membered aromatic ring is substituted with sulfonate orcarboxylate.
 5. The dye recited in claim 1, wherein R¹ or R² is an alkylof 1-10 carbon atoms substituted with a sulfonate or carboxylate and atleast one combination of R⁴ and R⁵ or R⁶ and R⁷ are taken together toform a six-membered aromatic ring or a 10membered aromatic ring whereinsaid six-membered aromatic ring or said 10-membered aromatic ring issubstituted with a sulfonate or a carboxylate.
 6. The dye recited inclaim 5, wherein R¹ or R² is an alkyl of 1-5 carbons atoms.
 7. The dyerecited in claim 8, wherein R³ is chosen from a group consisting ofbenzothiazole, pyrimidine, benzoxazole, phenyltetrazole, and methyltriazole.
 8. A dye of formula: ##STR12## wherein X¹ and X² independentlyrepresents --O--;n is an integer of 2 or 3; R¹ and R² independentlyrepresent alkyl of 1 to 10 carbons or an alkyl of 1 to 10 carbonssubstituted with at least one substituent chosen from a group consistingof sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl, amine, aryl or--OL¹, where L¹ is an alkyl of 1-10 carbons; R³ represents aheterocyclic ring containing atoms chosen from a group consisting of C,N, O, S and Se; R⁴ and R⁵ independently represent hydrogen, alkyl of1-10 carbons or an alkyl of 1-10 carbons substituted with at least onesubstituent chosen from a group consisting of sulfonate, carboxyl,hydroxy, halogen, carbonylalkyl, amine, aryl or --OL², where L² is analkyl of 1-10 carbons, or R⁴ and R⁵ taken together represent the atomsnecessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, an aromatic six-memberring substituted with at least one substituent chosen from a groupconsisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl,amine, aryl or --OL³, where L³ is an alkyl of 1-10 carbons, or anaromatic 10-member ring substituted with at least one substituent chosenfrom a group consisting of sulfonate, carboxyl, hydroxy, halogen,carbonylalkyl, amine, aryl or --OL⁴, where L⁴ is an alkyl of 1-10carbons; R⁶ and R⁷ independently represent hydrogen, alkyl of 1-10carbons or an alkyl of 1-10 carbons substituted with at least onesubstituent chosen from a group consisting of sulfonate, carboxyl,hydroxy, halogen, carbonylalkyl, amine, aryl or --OL⁵, where L⁵ is analkyl of 1-10 carbons, or R⁶ and R⁷ taken together represent atomsnecessary to form a 5 or 6-membered aliphatic ring, an aromaticsix-membered ring, an aromatic 10-membered ring, an aromatic six-memberring substituted with at least one substituent chosen from a groupconsisting of sulfonate, carboxyl, hydroxy, halogen, carbonylalkyl,amine, aryl or --OL⁶, where L⁶ is an alkyl of 1-10 carbons or anaromatic 10-member ring substituted with at least one substituent chosenfrom a group consisting of sulfonate, carboxyl, hydroxy, halogen,carbonylalkyl, amine, aryl or --OL⁷, where L⁷ is an alkyl of 1-10carbons; and Z is an anion or cation suitable to balance the charge. 9.The dye recited in claim 8, wherein at least one of R¹ and R² is analkyl of 1 to 10 carbon atoms substituted with sulfonate or carbonate.10. The dye recited in claim 8, wherein R⁴ and R⁵ or R⁶ and R⁷ are takentogether to form a six-membered aromatic ring or a 10-membered aromaticring.
 11. The dye recited in claim 10, wherein said six-memberedaromatic ring or said 10-membered aromatic ring is substituted withsulfonate or carboxylate.
 12. The dye recited in claim 8, wherein R¹ orR² is an alkyl of 1-10 carbon atoms substituted with a sulfonate orcarboxylate and at least one combination of R⁴ and R⁵ or R⁶ and R⁷ aretaken together to form a six-membered aromatic ring or a 10-memberedaromatic ring wherein said six-membered aromatic ring or said10-membered aromatic ring is substituted with a sulfonate or acarboxylate.
 13. The dye recited in claim 12, wherein R¹ or R² is analkyl of 1-5 carbons.